580
J. Chem. Eng. Data 1997, 42, 580-584
Static Relative Permittivities of Water + Acetone and Water + Dimethyl Sulfoxide under Pressures up to 300 MPa at 298.15 K Yasuhiro Uosaki,* Sunao Kitaura, and Takashi Moriyoshi Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Tokushima 770, Japan
Liquid phase static relative permittivities r of water + acetone and water + dimethyl sulfoxide have been measured over the whole mole-fraction range under pressures up to 300 MPa at 298.15 K. The pressure P dependence of r values for each mixture was well fitted to the Tait-type equation, and the Tait-type parameters, A and B, were determined. For each aqueous mixture, the composition dependence of (∂ ln r/∂P)T values at 0.1 MPa evaluated from the static relative permittivity at 0.1 MPa, r(0.1), and the Tait-type parameters was compared with that of the isothermal compressibility κT at 0.1 MPa. Values of r-2(∂r/∂P)T at 0.1 MPa as a function of composition were also compared for both aqueous mixtures. For pure acetone, (∂ ln r/∂P)T and r-2(∂r/∂P)T values at 0.1 MPa were correlated with temperature by a combination of the present values and the ones evaluated from the literature r data.
Introduction
Experimental Section
Acetone and dimethyl sulfoxide are versatile polar aprotic solvents, and each compound has the following chemical formula (CH3)2XdO; X ) C for acetone and X ) S for dimethyl sulfoxide. The static relative permittivity, wellknown as the dielectric constant, at 0.1 MPa and 298.15 K, r(0.1), for acetone is less than half of that for dimethyl sulfoxide, and there is a large difference in the dipole moment µ between these compounds (Riddick et al., 1986). Hence it is considered that the >SdO group in a dimethyl sulfoxide molecule is more polarizable than the >CdO group in an acetone molecule. As a result, there are some possibilities of difference in intermolecular interactions of dimethyl sulfoxide or acetone with water. Many studies on the thermodynamic properties have been done so far to get some insight into the interactions in these aqueous systems.
Acetone (Wako Pure Chemical Industries Ltd, >99%) was purified by the standard method (Riddick et al., 1986). Under a N2 stream at reduced pressure, dimethyl sulfoxide (Tokyo Kasei Kogyo Co. Ltd., >99%) was refluxed over CaH2 for several hours and then distilled. Water was purified by the method described earlier (Uosaki et al., 1996). Their purities were checked by comparing the measured refractive indices nD at 298.15 K with those reported in the literature (Riddick et al., 1986). All the mixtures were prepared by mass with a precision of 0.0001 g. The mole-fraction error is estimated to be less than 2 × 10-5. The procedure and apparatus for measuring r have been described in detail previously (Moriyoshi et al., 1990). Temperature was controlled to (0.01 K, and pressure was measured by a Bourdon gauge with an accuracy of 0.35 MPa. The uncertainty in r is estimated to be within (0.1%.
In a previous paper (Uosaki et al., 1996), we reported the pressure dependence of the static relative permittivities r of water + 1-methyl-2-pyrrolidinone and water + 1,3dimethyl-2-imidazolidinone in the liquid phase over the whole mole-fraction range under pressures up to 300 MPa at 298.15 K and evaluated (∂ ln r/∂P)T and r-2(∂r/∂P)T at 0.1 MPa as a function of composition for each mixture. We have so far reported the preliminary static permittivity results for water + acetone (Moriyoshi and Uosaki, 1984). In this work, we report not only the liquid phase static relative permittivities of water + dimethyl sulfoxide over the entire mole-fraction range under pressures up to 300 MPa at 298.15 K but also the newly-determined static relative permittivities for water + acetone under the same conditions. In addition, we correlate r values with pressure P by use of the Tait-type equation and we evaluate (∂ ln r/∂P)T and r-2(∂r/∂P)T values at 0.1 MPa, which are important for analyzing the thermodynamic properties of electrolyte solutions; some limiting partial molar volumes of electrolytes in water + acetone mixtures (Kawaizumi et al., 1988) and in water + dimethyl sulfoxide mixtures (Garcia-Paneda et al., 1996) have been reported. * To whom correspondence should
[email protected].
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Results and Discussion The r measurements were made more than twice for each solution, and the values were reproducible to within (0.1%. The averaged experimental values for water + acetone and water + dimethyl sulfoxide in the liquid phase at 298.15 K are listed in Table 1 as functions of P and the mole fraction of the organic component, x2. Some literature values of the static relative permittivities at 0.1 MPa and 298.15 K, r(0.1), for pure organic compounds are also included in Table 1 for comparison. Figures 1 and 2 show the r(0.1) values at 298.15 K for water + acetone and water + dimethyl sulfoxide as a function of composition, respectively. The literature r(0.1) values for each aqueous mixture are also plotted for comparison. The present r(0.1) values for water + acetone agree with the literature (Albright, 1937; Schiavo et al., 1979) within (0.8% over the whole mole-fraction range. For water + dimethyl sulfoxide, the literature values (Lindberg and Kentta¨maa, 1960; Douheret and Morenas, 1967; Tommila and Pajunen, 1968; Schiavo et al., 1979) are also in agreement with ours within (0.8%. Figures 3 and 4 show the pressure dependence of the experimental r results for each solution. With increasing © 1997 American Chemical Society
Journal of Chemical and Engineering Data, Vol. 42, No. 3, 1997 581 Table 1. Static Relative Permittivities Er for Water + Acetone and Water + Dimethyl Sulfoxide as a Function of Pressure at 298.15 K P/MPa x2
0.1
0.200 0.400 0.600 0.800 1
53.56 38.76 30.07 24.63 20.74 20.74a 20.56b
0.200 0.400 0.600 0.800 1
74.33 67.78 60.08 52.94 46.41 46.60b 46.35c 46.45d
a
10
20
30
40
50
100
125
Water (1) + Acetone (2) 55.15 56.54 40.39 41.69 31.59 32.76 26.05 27.10 22.06 23.00
46.54
46.67
Water (1) + Dimethyl Sulfoxide (2) 75.85 77.22 69.13 70.30 61.21 62.13 53.79 54.48 54.77 46.80 46.91 47.02
Albright, 1937. b Schiavo et al., 1979. c Douheret and Morenas, 1967.
Figure 1. Static relative permittivities at 0.1 MPa and 298.15 K, r(0.1), against mole fraction, x2, for water (1) + acetone (2) (b, this work; O, Albright, 1937; 4, Schiavo et al., 1979).
pressure, r increases and (∂r/∂P)T becomes smaller. Some dimethyl sulfoxide solutions froze at high pressures. It is considered that the r datum for pure dimethyl sulfoxide at 50 MPa and 298.15 K is the value under the superpressed state. After the capacitance measurements at 50 MPa were finished, the pressure was increased at the rate of about 3 MPa/min. Near 60 MPa, a sudden drop of the pressure to about 32 MPa was found because of the freezing of dimethyl sulfoxide. Compared with the estimated freezing pressure Pf, 40.9 MPa, at 298.15 K from the Simon equation (Fuchs et al., 1980), the present value is relatively low. The pressure difference is mainly caused by the freezing of dimethyl sulfoxide that occurred in an endothermic process, so the temperature of dimethyl sulfoxide in a dielectric cell should be slightly lower than the temperature of 298.15 K; an estimated temperature of dimethyl sulfoxide at that pressure from the Simon equation is about 296.8 K, which is about 1.4 K lower than a water-bath temperature. In an aqueous dimethyl sulfoxide
d
150
200
250
300
57.76 42.79 33.71 27.94 23.77
58.87 43.75 34.53 28.66 24.40
59.88 44.61 35.26 29.30 24.96
60.81 45.39 35.91 29.87 25.45
78.44 71.34 62.93 55.05
79.57 72.27 63.63
80.60 73.12 64.23
81.57 73.90 64.78
Casteel and Sears, 1974.
Figure 2. Static relative permittivities at 0.1 MPa and 298.15 K, r(0.1), against mole fraction, x2, for water (1) + dimethyl sulfoxide (2) (9, this work; 0, Lindberg and Kentta¨maa, 1960; 2, Douheret and Morenas, 1967; 4, Tommila and Pajunen, 1968; 3, Schiavo et al., 1979).
mixture of the composition x2 ) 0.800, the pressure drop from 170 MPa to 160 MPa was also found. To correlate the pressure dependence of the r data for each solution, we used the Tait-type equation of the form
1-
r(0.1) r(P)
(B B+ +P/MPa 0.1 )
) A ln
(1)
where r(P) is the static relative permittivity at the pressure P. The Tait-type parameters, A and B, for each solution, which were determined from the nonweighted least-squares method, are summarized in Table 2, along with the standard deviations σ(r) of the fit. Furthermore, Table 2 includes the results for pure water (Moriyoshi et al., 1990). In any solution the σ(r) values in the present work are less than 0.01, which is within the experimental uncertainty and the reproducibility. Hence, the r(P) value
582 Journal of Chemical and Engineering Data, Vol. 42, No. 3, 1997 Table 2. Static Relative Permittivity at 0.1 MPa, Er(0.1), Parameters of the Tait-Type Equation, A and B, and Standard Deviations, σ(Er)
Figure 4. Pressure dependence of the static relative permittivities, r, for water (1) + dimethyl sulfoxide (2) at 298.15 K. The smoothed curves are based on the parameters A and B in Table 2.
at any pressure up to the maximum pressure Pmax can be evaluated very precisely from the Tait-type equation. Since Hartmann et al. (1965a) reported r values of acetone up to 182.4 MPa at three temperatures, 293.15 K, 308.15 K, and 323.15 K, we also included the Tait-type parameters in Table 2, which were determined from their results; they applied some equations to analyze their r data and reported some parameters similar to the Tait-type parameters (Hartmann et al., 1965b). The (∂ ln r/∂P)T and r-2(∂r/∂P)T values are respectively needed to obtain the thermodynamic properties such as the partial molar volume of electrolytes at infinite dilution from the apparent partial molar volume and to analyze the contribution of the electrostriction to the partial molar volume of an individual ion. These values at 0.1 MPa can
Pmaxa/MPa
0.02 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01
300.0 300.0 300.0 300.0 300.0 182.4 300.0 182.4 182.4
Water (1) + Dimethyl Sulfoxide (2) 298.15 74.33 0.1194 271.8 0.01 298.15 67.78 0.09842 227.1 0.00 298.15 60.08 0.07063 166.8 0.01 298.15 52.94 0.05617 153.1 0.00 298.15 46.41 0.04750 158.4 0.01
300.0 300.0 300.0 150.0 50.0
T/K
0b 0.200 0.400 0.600 0.800 1
298.15 298.15 298.15 298.15 298.15 293.15c 298.15 308.15c 323.15c
0.200 0.400 0.600 0.800 1
Figure 3. Pressure dependence of the static relative permittivities, r, for water (1) + acetone (2) at 298.15 K. The smoothed curves are based on the parameters A and B in Table 2.
σ(r)
x2
r(0.1)
A
B
Water (1) + Acetone (2) 78.41 0.2185 463.6 53.56 0.1311 202.0 38.76 0.1182 122.9 30.07 0.1143 95.1 24.63 0.1131 80.7 21.24 0.1043 68.4 20.74 0.1115 70.3 19.75 0.1085 62.1 18.34 0.1047 49.0
a Maximum pressure applicable to estimate (P) values from r the values of r(0.1), A, and B by the Tait-type equation. b The data at this composition are cited from the literature (Moriyoshi et al., 1990). c At these temperatures the r(0.1), A, and B values are based on the r data (Hartmann et al., 1965a).
Figure 5. Composition dependence of (∂ ln r/∂P)T and κT at 0.1 MPa and 298.15 K for water (1) + acetone (2) (b, O) and water (1) + dimethyl sulfoxide (2) (9, 0). Closed and open symbols represent (∂ ln r/∂P)T and κT, respectively. The κT value for dimethyl sulfoxide at 0.1 MPa and 298.15 K (4) is cited from the literature (Tamura et al., 1994).
be evaluated from r(0.1) and the Tait-type parameters as follows:
( ) ( )
r-2
∂ ln r ∂P
T
A B + 0.1
(2)
∂r ∂P
A r(0.1)(B + 0.1)
(3)
)
T
)
For brevity we used r for r(P) in these equations. Figure 5 shows the composition dependence of the calculated (∂ ln r/∂P)T values at 0.1 MPa and 298.15 K for each aqueous mixture, together with the isothermal compressibility, κT ) -(∂ ln V/∂P)T, at 0.1 MPa and 298.15 K,
Journal of Chemical and Engineering Data, Vol. 42, No. 3, 1997 583
r-2(∂r/∂P)T
Figure 6. Composition dependence of at 0.1 MPa and 298.15 K for water (1) + acetone (2) (b) and water (1) + dimethyl sulfoxide (2) (9).
because a rough correlation between (∂ ln r/∂P)T and κT values has been suggested without a theoretical basis (Kawaizumi and Zana, 1974). From the compression measurements, the κT values for water + acetone over the whole mole-fraction range and those for water + dimethyl sulfoxide in the composition range x2 ) 0-0.5 have been obtained (Moriyoshi and Uosaki, 1984). The κT value for pure dimethyl sulfoxide was taken from the literature (Tamura et al., 1994). For water + acetone, there is a slight resemblance of the composition dependence of (∂ ln r/∂P)T and κT values, but (∂ ln r/∂P)T values are larger than κT values over the whole composition range; the largest deviation is found at x2 ) 0.6, and its value is about 23%. For water + dimethyl sulfoxide, the (∂ ln r/∂P)T values decrease with the composition, while the κT values show a minimum at x2 ) 0.2; the composition dependence of (∂ ln r/∂P)T values is very different from that of κT values. Also in this system, a large difference in magnitude between these values is found; the (∂ ln r/∂P)T value for pure dimethyl sulfoxide is 76% less than the κT value. From the previous paper (Uosaki et al., 1996) and the present results, it should be noted that the use of κT values to estimate the (∂ ln r/∂P)T values gives unreliable results. The r-2(∂r/∂P)T values as a function of x2 are shown in Figure 6. The values for water + acetone increase from 6.01 at x2 ) 0 to 76.36 at x2 ) 1, while those for water + dimethyl sulfoxide vary only between about 6 and 7 and show no significant composition dependence. The static relative permittivities for pure acetone under high pressures have been reported at three temperatures, 293.15 K, 308.15 K, and 323.15 K (Hartmann et al., 1965a). Estimated (∂ ln r/∂P)T and r-2(∂r/∂P)T values at 0.1 MPa from their data are plotted against temperature in Figure 7, together with our results at 298.15 K. The values in the temperature range of 293.15 K to 323.15 K are well represented by the following equation:
X/TPa-1 ) A0 + A1(T/K) + A2(T/K)2
(4)
where X is (∂ ln r/∂P)T or r-2(∂r/∂P)T. Table 3 gives the parameters Aj, along with the standard deviation σ(X) of
Figure 7. Temperature dependence of (∂ ln r/∂P)T and r-2(∂r/ ∂P)T at 0.1 MPa for acetone (b, this work; O, Hartmann et al., 1965a). Table 3. Coefficients Aj and Standard Deviation σ(X) for Least-Squares Representations of (D ln Er/DP)T and Er-2(DEr/ DP)T for Acetone by Eq 4 X/TPa-1
A1
A2
A3
σ(X)
(∂ ln r/∂P)T r-2(∂r/∂P)T
30082 1986.8
-204.16 -13.802
0.36412 0.024797
4.7 0.38
the fit. In each case, the σ(X) value is small enough to evaluate the values accurately at any temperature between 293.15 K and 323.15 K. Literature Cited Albright, P. S. Experimental Tests of Recent Theories Descriptive of the Salting-out Effect. J. Am. Chem. Soc. 1937, 59, 2098-2104. Casteel, J. F.; Sears, P. G. Dielectric Constants, Viscosities, and Related Physical Properties of 10 Liquid Sulfoxides and Sulfones at Several Temperatures. J. Chem. Eng. Data 1974, 19, 196-200. Douheret, G.; Morenas, M. Dielectric Constants of Some Aqueousorganic Mixtures. C. R. Acad. Sci. Paris, Ser. C 1967, 264, 729731 (in French). Fuchs, A. H.; Ghelfenstein, M.; Szwarc, H. Melting Curve and PressureVolume-Temperature Data of Liquid Dimethyl Sulfoxide up to 150 MPa. J. Chem. Eng. Data 1980, 25, 206-208. Garcia-Paneda, E.; Yanes, C.; Munoz de Miguel, E.; Maestre, A. Limiting Partial Molar Volumes of Tetra-n-alkylammonium Bromides in Dimethyl Sulfoxide + Water Mixtures at 298.15 K. J. Chem. Eng. Data 1996, 41, 1149-1151. Hartmann, H.; Neumann, A.; Rinck, G. Pressure Dependence of the Dielectric Constants of Some Organic Liquids. Z. Phys. Chem. N. F. 1965a, 44, 204-217 (in German). Hartmann, H.; Neumann, A.; Rinck, G. Analytic Description of the Pressure Dependence of the Dielectric Constants of Liquids. Z. Phys. Chem. N. F. 1965b, 44, 218-226 (in German). Kawaizumi, F.; Zana, R. Partial Molal Volumes of Ions in Organic Solvents from Ultrasonic Vibration Potentials and Density Measurements. II. Ethanol and Dimethylformamide. J. Phys. Chem. 1974, 78, 1099-1105. Kawaizumi, F.; Nakao, F.; Nomura, H. Partial Molar Volumes and Compressibilities of 1-1 Type Chlorides, Bromides, [Ph4P]Cl, and [Ph4B] in Water-Acetone Mixtures. J. Chem. Eng. Data 1988, 33, 204-211. Lindberg, J. J.; Kentta¨maa, J. Some Considerations of the Structure of Dimethyl Sulfoxide-Water Mixtures in the Light of Thermodynamic and Dielectric Behavior. Suom. Kemist. 1960, B33, 104-107. Moriyoshi, T.; Uosaki, Y. Compressive and Dielectric Properties of Aqueous Non-Electrolyte Mixtures. J. Soc. Mater. Sci. Jpn. 1984, 33, 127-133 (in Japanese). Moriyoshi, T.; Ishii, T.; Tamai, Y.; Tado, M. Static Dielectric Constants of Water + Ethanol and Water + 2-Methyl-2-propanol Mixtures from 0.1 to 300 MPa at 298.15 K. J. Chem. Eng. Data 1990, 35, 17-20.
584 Journal of Chemical and Engineering Data, Vol. 42, No. 3, 1997 Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents, 4th ed.; Wiley-Interscience: New York, 1986. Schiavo, S.; Fuoss, R. M.; Marrosu, G.; Guida, G. Ion Pairing of Quaternary Salts in Solvent Mixtures. J. Solution Chem. 1979, 8, 557-571. Tommila, E.; Pajunen, A. The Dielectric Constants and Surface Tensions of Dimethyl Sulphoxide-Water Mixtures. Suom. Kemist. 1968, B41, 172-176. Tamura, K.; Murakami, S.; Akagi, Y.; Fukumori, M.; Kawasaki, Y. Thermodynamic Properties of Binary Mixtures: Hexamethylphosphoric Triamide + a Polar Liquid at 25 °C. J. Solution Chem. 1994, 23, 263-273.
Uosaki, Y.; Kawamura, K.; Moriyoshi, T. Static Relative Permittivities of Water + 1-Methyl-2-pyrrolidinone and Water + 1,3-Dimethyl-2imidazolidinone Mixtures under Pressures up to 300 MPa at 298.15 K. J. Chem. Eng. Data 1996, 41, 1525-1528. Received for review December 4, 1996. 1997.X
Accepted February 12,
JE960390Y X
Abstract published in Advance ACS Abstracts, April 1, 1997.
